Determination of seven heterocyclic aromatic amines in oils and fried foods by ultra performance liquid chromatography-triple quadrupole mass spectrometry

doi:10.3724/SP.J.1123.2019.04046

Abstract

Abstract:

An ultra performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-MS/MS) method was developed for the determination of seven heterocyclic aromatic amines (HCAs) in oil and fried food samples. The samples were extracted with acetonitrile containing 1% (v/v) ammonia water, defatted by n-hexane saturated with acetonitrile, and cleaned up with PCX solid phase extraction column. The extracts were separated on a Waters ACQUITY UPLC BEH C18 reversed-phase column (50 mm×2.1 mm, 1.7 μm) with gradient elution by using acetonitrile-10 mmol/L ammonium formate aqueous solution as the mobile phase. Quantitative detection was performed by using a positive-ion electrospray ionization source in the multiple reaction monitoring (MRM) mode, employing an internal isotope standard. The method showed good linear relationships in the range of 0.5-100 μg/L for the seven HCAs with correlation coefficients (R²)>0.999. The average recoveries ranged from 64.31% to 113.8% with the relative standard deviations of 0.18%-9.26% at the three spiked levels in oil and fried food samples. The limits of detection (LODs) and limits of quantification (LOQs) were 0.01-0.14 ng/g and 0.09-0.38 ng/g, respectively. The method is sensitive, accurate, and suitable for the determination and confirmation of the seven HCAs in oil and fried food samples.

Key words: ultra performance liquid chromatography (UPLC), triple quadrupole mass spectrometry (MS/MS), solid phase extraction (SPE), heterocyclic aromatic amines (HCAs), oils, fried foods

ZHANG Chenxia, MA Yuxiang, ZHAO Tianpei, XI Jun, LI Pan, GUO Qing, SHI Lili, WANG Xuede. Determination of seven heterocyclic aromatic amines in oils and fried foods by ultra performance liquid chromatography-triple quadrupole mass spectrometry[J]. Chinese Journal of Chromatography, 2020, 38(2): 224-231.

Figures/Tables 7

References

1	Li Y , He Z Y , Gao D M , et al. Journal of Food Safety and Quality, 2019, 10 (2): 312
1	李永, 何志勇, 高大明, et al. 食品安全质量检测学报, 2019, 10 (2): 312
2	Sugimura T . Mutat Res-Fund Mol M, 1985, 150 (1): 33
3	Bellamri M , Turesky R J . Encyclo of Food Chem, 2019 550
4	Delannee V , Langouet S , Siegel A , et al. Toxicol Lett, 2019, 300: 18
5	Xie Y Y , Wang X X , Yan W J , et al. Food Research and Development, 2017, 38 (15): 199
5	谢洋洋, 王小溪, 闫文杰, et al. 食品研究与开发, 2017, 38 (15): 199
6	Xiao S , Guo J , Yun B H , et al. Anal Chem, 2016, 88 (24): 12508
7	Turesky R J , Paul V . J Chromatogr B, 2004, 802 (1): 155
8	Niwa T , Yamazoe Y , Kato R . Mutat Res, 1982, 95 (2/3): 159
9	Ito N , Hasegawa R , Sano M , et al. Carcinogenesis, 1991, 12 (8): 1503
10	Jian S H , Yeh P J , Wang C H , et al. J Food Drug Anal, 2019, 27 (2): 595
11	Barzegar F , Kamankesh M , Mohammadi A . Food Chem, 2019, 280: 240
12	Kato T , Ohgaki H , Hasegawa H , et al. Carcinogenesis, 1988, 9 (1): 71
13	Wong D , Cheng K W , Wang M . Food Chem, 2012, 133 (3): 760
14	Gross G A , Grüter A . J Chromatogr A, 1992, 592 (1/2): 271
15	Skog K . Food Chem Toxicol, 2002, 40 (8): 1197
16	Gibis M . Compr Rev Food Sci F, 2016, 15 (2): 269
17	Wolk A . J Intern Med, 2017, 281 (2): 106
18	Wang Y , Hui T , Zhang Y W , et al. Food Chem, 2015, 167: 251
19	Fei L , Kuhnle G K , Cheng Q . Food Control, 2018, 92: 399
20	Zamora R , Hidalgo F J . Rsc Adv, 2015, 5 (13): 9709
21	Solyakov A , Skog K . Food Chem Toxicol, 2002, 40 (8): 1205
22	Johansson M , Skog K , JGerstad M. Carcinogenesis, 1993, 14 (1): 89
23	Jinap S , Mohd Mokhtar M S , Farhadian A , et al. Meat Sci, 2013, 94 (2): 202
24	Zamora R , Alcón E , Hidalgo F J . Food Chem, 2012, 135 (4): 2569
25	Shao B , Peng Z Q , Yang H S , et al. Chinese Journal of Chromatography, 2011, 29 (8): 755
25	邵斌, 彭增起, 杨洪生, et al. 色谱, 2011, 29 (8): 755
26	Turesky R J , Jason T , Laura S , et al. J Agric Food Chem, 2005, 53 (8): 3248
27	Guo H T , Pan H , Wang Z Y , et al. Chinese Journal of Chromatography, 2012, 30 (10): 1074
27	郭海涛, 潘晗, 王振宇, et al. 色谱, 2012, 30 (10): 1074
28	Xian Y P , Wu Y L , Dong H , et al. Food Chem, 2019, 285: 77
29	Zhang W F , Lan C , Zhang H M . J Agric Food Chem, 2019, 67 (13): 3733
30	Barceló-Barrachina E , Moyano E , Galceran M T , et al. J Chromatogr A, 2006, 1125 (2): 195
31	Zhang Y , Lin C , Fang G , et al. Eur Food Res Technol, 2012, 234 (2): 197
32	Zhang Q C , Xiao X H , Li G K . Chinese Journal of Chromatography, 2014, 32 (9): 975
32	张仟春, 肖小华, 李攻科. 色谱, 2014, 32 (9): 975
33	Yan Y , Zeng M , Zheng Z , et al. Anal Methods, 2014, 6 (16): 6437
34	Yan Y , Zhang S , Tao G J , et al. J Chromatogr B, 2017, 1068: 173
35	Shi L K , Liu Y L . Journal of the Chinese Cereals and Oils Association, 2015, 30 (12): 114
35	石龙凯, 刘玉兰. 中国粮油学报, 2015, 30 (12): 114
36	Liu Z C , Yang F , Yu K J , et al. Chinese Journal of Chromatography, 2012, 30 (12): 1253
36	刘正才, 杨方, 余孔捷, et al. 色谱, 2012, 30 (12): 1253
37	Matuszewski B K , Constanzer M L , Chavez-Eng C M . Anal Chem, 1998, 70 (5): 882

Compound	Parent ion (m/z)	Cone voltage (CV)/V	Product ion pair (m/z)	Collision energies (CEs)/eV
* Quantitative ion.
2-amino-3-methylimidazo[4, 5-f]quinoline (IQ)	199.09	58	199.09/184.03^*, 199.09/156.99	26, 30
2-amino-3, 4-dimethylimidazo[4, 5-f]quinoline (MeIQ)	213.11	58	213.11/198.05^*, 213.11/144.04	24, 40
2-amino-3, 8-dimethyl-imidazo[4, 5-f]-quinoxaline (MeIQx)	214.12	54	214.12/199.04^*, 214.12/130.99	24, 36
2-amino-3, 4, 8-trimethyl-imidazo[4, 5-f]-quinoxaline (4, 8-DiMeIQx)	228.13	40	228.13/213.10^*, 228.13/212.99	25, 34
2-amino-3, 4, 7, 8-tetramethylimidazo[4, 5-f]quinoxaline	242.16	62	242.16/227.00^*, 242.16/145.03	28, 40
(4, 7, 8-TriMeIQx) (IS)
2-amino-1-methyl-6-phenylimidazo[4, 5-b]-pyridine (PhIP)	225.11	54	225.11/210.04^*, 225.11/114.75	42, 50
1-methyl-9H-pyrido[3, 4-b]indole (Harman)	183.01	56	183.01/114.97^*, 183.01/142.03	40, 26
9H-pyrido[3, 4-b]indole (Norharman)	169.03	56	169.03/114.96^*, 169.03/168.11	34, 24

Compound	Parent ion (m/z)	Cone voltage (CV)/V	Product ion pair (m/z)	Collision energies (CEs)/eV
* Quantitative ion.
2-amino-3-methylimidazo[4, 5-f]quinoline (IQ)	199.09	58	199.09/184.03^*, 199.09/156.99	26, 30
2-amino-3, 4-dimethylimidazo[4, 5-f]quinoline (MeIQ)	213.11	58	213.11/198.05^*, 213.11/144.04	24, 40
2-amino-3, 8-dimethyl-imidazo[4, 5-f]-quinoxaline (MeIQx)	214.12	54	214.12/199.04^*, 214.12/130.99	24, 36
2-amino-3, 4, 8-trimethyl-imidazo[4, 5-f]-quinoxaline (4, 8-DiMeIQx)	228.13	40	228.13/213.10^*, 228.13/212.99	25, 34
2-amino-3, 4, 7, 8-tetramethylimidazo[4, 5-f]quinoxaline	242.16	62	242.16/227.00^*, 242.16/145.03	28, 40
(4, 7, 8-TriMeIQx) (IS)
2-amino-1-methyl-6-phenylimidazo[4, 5-b]-pyridine (PhIP)	225.11	54	225.11/210.04^*, 225.11/114.75	42, 50
1-methyl-9H-pyrido[3, 4-b]indole (Harman)	183.01	56	183.01/114.97^*, 183.01/142.03	40, 26
9H-pyrido[3, 4-b]indole (Norharman)	169.03	56	169.03/114.96^*, 169.03/168.11	34, 24

Compound	Linear range/ (μg/L)	Linear equations (R²)			LOD/ (ng/g)	LOQ/ (ng/g)
Compound	Linear range/ (μg/L)	Methanol solution	Soybean oil	Fried food	LOD/ (ng/g)	LOQ/ (ng/g)
y: the ratio of the peak area of the target component to the peak area of the internal standard; x: the ratio of the mass concentration of the target component to the mass concentration of the internal standard.
IQ	0.5-20	y=0.1003x-0.0065 (0.9999)	y=0.0955x-0.0161 (0.9995)	y=0.1015x-0.0133 (0.9999)	0.03	0.15
MeIQ	0.5-2020	y=0.1104x-0.0041 (0.9997)	y=0.0932x-0.0073 (0.9999)	y=0.0916x-0.0093 (0.9995)	0.14	0.20
MeIQx	0.5-2020	y=0.0417x-0.0055 (0.9998)	y=0.0429x+0.0006 (0.9993)	y=0.0406x-0.0036 (0.9997)	0.13	0.38
4, 8-DiMeIQx	0.5-2020	y=0.0484x+0.0009 (0.9997)	y=0.0512x-0.0135 (0.9994)	y=0.0479x-0.0011 (0.9994)	0.01	0.09
PhIP	1-100	y=0.0151x-0.0007 (0.9993)	y=0.0179x+0.0026 (0.9991)	y=0.0162x+0.0025 (0.9998)	0.01	0.09
Harman	1-100	y=0.1157x-0.0022 (0.9999)	y=0.0967x-0.0108 (0.9996)	y=0.0876x-0.0152 (0.9992)	0.05	0.16
Norharman	1-100	y=0.1366x+0.0402 (0.9998)	y=0.1233x+0.0287 (0.9999)	y=0.0989x-0.0019 (0.9996)	0.14	0.24

Compound	Linear range/ (μg/L)	Linear equations (R²)			LOD/ (ng/g)	LOQ/ (ng/g)
Compound	Linear range/ (μg/L)	Methanol solution	Soybean oil	Fried food	LOD/ (ng/g)	LOQ/ (ng/g)
y: the ratio of the peak area of the target component to the peak area of the internal standard; x: the ratio of the mass concentration of the target component to the mass concentration of the internal standard.
IQ	0.5-20	y=0.1003x-0.0065 (0.9999)	y=0.0955x-0.0161 (0.9995)	y=0.1015x-0.0133 (0.9999)	0.03	0.15
MeIQ	0.5-2020	y=0.1104x-0.0041 (0.9997)	y=0.0932x-0.0073 (0.9999)	y=0.0916x-0.0093 (0.9995)	0.14	0.20
MeIQx	0.5-2020	y=0.0417x-0.0055 (0.9998)	y=0.0429x+0.0006 (0.9993)	y=0.0406x-0.0036 (0.9997)	0.13	0.38
4, 8-DiMeIQx	0.5-2020	y=0.0484x+0.0009 (0.9997)	y=0.0512x-0.0135 (0.9994)	y=0.0479x-0.0011 (0.9994)	0.01	0.09
PhIP	1-100	y=0.0151x-0.0007 (0.9993)	y=0.0179x+0.0026 (0.9991)	y=0.0162x+0.0025 (0.9998)	0.01	0.09
Harman	1-100	y=0.1157x-0.0022 (0.9999)	y=0.0967x-0.0108 (0.9996)	y=0.0876x-0.0152 (0.9992)	0.05	0.16
Norharman	1-100	y=0.1366x+0.0402 (0.9998)	y=0.1233x+0.0287 (0.9999)	y=0.0989x-0.0019 (0.9996)	0.14	0.24

Compound	Added/ (ng/g)	Soybean oil		Fried chicken breast
Compound	Added/ (ng/g)	Recovery/ %	RSD/ %	Recovery/ %	RSD/ %
IQ	1	70.93	4.30	76.05	7.89
	10	69.30	3.34	91.04	2.51
	20	80.30	0.97	98.41	1.99
MeIQ	1	78.31	6.43	65.67	7.48
	10	84.77	1.59	96.46	2.58
	20	82.42	1.03	104.5	1.29
MeIQx	1	71.68	9.26	75.73	0.18
	10	74.51	3.35	64.31	3.11
	20	104.8	1.11	109.4	2.17
4, 8-DiMeIQx	1	91.41	5.64	65.75	3.62
	10	84.47	4.21	88.79	1.60
	20	97.80	1.31	90.63	2.05
PhIP	1	86.19	7.66	82.92	4.56
	20	97.50	4.03	95.09	3.95
	100	93.67	1.36	84.51	1.19
Harman	1	99.12	3.17	92.56	0.43
	20	95.42	3.91	109.3	5.77
	100	108.4	1.11	68.46	1.28
Norharman	1	78.31	5.74	113.8	4.16
	20	106.5	2.00	102.9	1.84
	100	83.59	1.02	94.67	1.63